Ca(OH)2 -treated ceramic microsphere

ABSTRACT

Geothermal wells with lost circulation problems are treated with a lightweight, high temperature (i.e. 350° C.) cement slurry which incorporates pressure resistant hollow microspheres into the slurry wherein the spheres have been pretreated with an alkali compound such as Ca(OH) 2  for up to 20 hours and at 100°-300° C. Preferably, the alkali solution is a saturated aqueous solution and the treatment is for 10 hours.

This invention was made with Government support under Contract NumberDE-AC02-76CH00016 awarded by the Department of Energy. The Governmenthas certain rights in this invention.

This is a divisional application of co-pending application Ser. No.106,269 filed Oct. 9, 1987, which issued as U.S. Pat. No. 4,822,422 onApr. 18, 1989.

BACKGROUND

The use of normal-density 14 to 15.8 lb/gal (1.7 to 1.9 g/cc) cementingslurries in completing geothermal and oil wells frequently results inproblems of lost circulation when attempts are made to cement wellregions that pass through weak unconsolidated rock zones having veryfragile gradients. Specifically, these unconsolidated formationsfracture as a result of the high hydrostatic pressures required to pumpthe highly dense cement slurries. To avoid this problem,high-temperature low-density cement slurries are needed to support theintermediate casing pipe and to protect the casing from corrosive fluidsand gases.

One method for the preparation of lightweight cement slurries which canbe used in geothermal and oil wells is to incorporatepressure-resistance hollow microspheres into cement slurries [Martin,Proceedings of the Third International Seminar of EC Geothermal EnergyResearch, Munich, Germany, p. 447, (1983)]. In addition to producing alightweight slurry, the relatively high bridging ability of the hollowbeads enhances its effectiveness in controlling lost-circulationproblems.

However, experience with microsphere-filled lightweight cement systemssuggests that the inclusion of the microspheres as a filler is notsufficient to yield to properties needed for geothermal cements. Forinstance, when a slurry with a density of 1.16 g/cc is autoclaved for 24hours at a temperature of 300° C. and a hydrostatic pressure of 1500 psi(10.3 MPa), the compressive strength of the set cement paste is only 610psi (4.2 MPa). The low strength is presumed to be due to poor bonding atthe cement-microsphere interface, and a low degree of hydration in thecement matrixes and the interfacial regions. Therefore, modification ofthe microsphere surfaces was necessary to produce a high-quality hightemperature lightweight cementing material that could meet the criteriaestablished for geothermal cements. The most important of these criteriaare a slurry density of <1.2 g/cc at 25° C., a 300° C.-24 hourcompressive strength of >1000 psi (6.9 MPa), and a bulk density of <1.0g/cc.

BRIEF DESCRIPTION OF THE INVENTION

The present invention relates to surface preparation techniques for thepressure-resistant ceramic hollow microspheres used as fillers ingeothermal cements which render the microspheres reliable in developingthe desired high strengh of the geothermal and oil well cementingmaterials at a temperature of up to 350° C.

The lightweight filler used in this invention is a pressure-resistantceramic hollow microsphere, having an average particle size ofapproximately 125 μm and a bulk density of approximately 0.4 g/cc. Thesurface modification of the microspheres is accomplished as follows: Themicrosphere surfaces are first rinsed with deionized water to remove anycontamination and then exposed for up to 20 hours to a saturatedsolution of an alkali earth metal hydroxide, preferably Ca(OH)₂, at ahigh temperature between 100° and 300° C. The preferred treatmentregimen is 100° C. for 10 hours. The microspheres are then washed againin deionized water and subsequently dired in an over at temperaturesaround 110° C.

API class H cement was used as the matrix since it has good strengthchracteristics at bottom-hole static temperatures >110° C. Table 1 belowshows the composition of a lightweight cement composite containing thesurface-treated microsphere of the present invention. Typical chemicalanalysis of the class H cement, supplied by the Lehigh Portland CementCompany, that was used in preparing the geothermal cements using thetreated microspheres of the present invention is given in Table 2.

                  TABLE 1                                                         ______________________________________                                        Composition                                                                   Class H  Silica,      Water,                                                  Cement,  flour        (W)     Microsphere                                     (C) wt % (S) wt %     wt %    wt %                                            ______________________________________                                        30       10           35      25                                              ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Composition, wt %                                                                                                      Loss on                              SiO.sub.2 CaO    Al.sub.2 O.sub.3                                                                      Fe.sub.2 O.sub.3                                                                    MgO  SO.sub.3                                                                           Ignition                             ______________________________________                                        Class H                                                                              22.40  64.40  4.29  4.92  0.80 2.20 0.40                               ______________________________________                                    

DESCRIPTION OF THE FIGURES

FIG. 1 shows an x-ray powder diffraction (XRD) pattern of shell materialin "as-received" hollow microspheres.

FIG. 2 shows and x-ray photoelectron spectroscopy (XPS) survey-scanspectra for untreated, 200° C. deionized water-treated, and 100° C.Ca(OH)₂ -treated spheres.

DETAILED DESCRIPTION OF THE INVENTION

The compressive strength and water permeability of high temperaturelightweight cementing meterials containing pressure resistantsillimanite-based hollow microspheres as a filler can be improved bytreating the surfaces of the microspheres with a Ca(OH)₂ solution atelevated temperatures in the range of from 100° C. to 300° C. Analysisof the chemical constituents of the preferred sillimanite-basedmicrospheres by x-ray powder diffraction analysis (XRD) showed thepresence of sillimanite, [represented interchangeably as Al(AlSiO₅) andAl₂ SiO₅ ], and quartz, so that the shell structure of the hollowmicrospheres appears to be an assembly of hybrid phases of sillimaniteand silica glass. FIG. 1 shows the XRD pattern of the untreatedmicrosphere shell. The treated surface of the sillimanite-based sphereplays an essential role in developing favorable bonding characteristicsat the interfaces and in promoting the hydration of the cement matrix.Bonding is associated with the formation of an intermediate layer ofaluminum-rich calcium silicate hydrate, produced by an interfacialreaction of the cement paste with the epitaxy, under the hydrothermalenvironment at temperatures around 300° C. A dense intermediate layerconsisting of a rim structure of approximately 4 μm thickness acts incross-linking and coupling functions that serve to connect the cementmatrix and spheres, thereby improving the interfacial bond strength. Thepresence of the epitaxial layer on the treated sphere surfaces leads tothe formation of a well-crystallized tobermorite matrix phase, which isresponsible for the development of strength in the lightweight cementsincorporating the treated microspheres.

The following empirical evidence is drawn for the interaction at theinterface between the sphere surface and the Ca(OH)₂ solution, and forthe formation of its reaction products at the interface. When thesillimanite-based microspheres are exposed to the alkaline Ca(OH)₂-saturated solution at 100° C., more silicate and aluminate is dissolvedfrom the sphere surface as an essential first step in the chemicalreaction. This dissolution significantly promotes the precipitation ofepitaxial CaO-SiO₂ -H₂ O and CaO-Al₂ O₃ -SiO₂ -H₂ O formations, producedby the chemical reactions between the dissociated Si and Al with theabundant Ca ions released from the Ca(OH)₂ solution. With increasedhydration, the precipitated layer is overlapped by these epitaxialhydration products. While the epitaxies grow is vicinity of the spheresurface, the unreactive Ca(OH)₂ also precipitates in the contact layerformed at the intefacial regions between the spheres and the reactionproducts. However, the deposited Ca(OH)₂ is masked entirely within thehydrated reaction product layers. Finally, the continuous contact layerforms a spherical shell structure to fully encapsulate the sphere.

EXAMPLE

The lightweight filler used was pressure-resistant, sillimanite-basedhollow microspheres having an average particle size of approximately 125μm and a bulk density of 0.4 g/cc, supplied by Fillite U.S.A., Inc. Themicrospheres ranged in size from approximately 30 to approximately 200μm, and it was estimated from profiles of fragments from fracturedspheres that the wall thickness was approximately 10 μm. An API class Hcement, supplied by the Lehigh Portland Cement Co., was used as thematrix. A typical analysis of the cement was: 64.4 wt. % CaO, 22.4 wt. %SiO₂, 4.29 wt. % Al₂ O₃, 4.29 wt. % Fe₂ O₃, 0.8 wt. % MgO, and 2.2 wt. %SO₃. To prevent retrogression of strength at high temperatures, silicaflour having a particle size of <44 μm was added to the cement.

The surface modification of the microspheres was accomplished asfollows. The microsphere surfaces first were rinsed with deionized waterto remove any contamination and then exposed for approximately 20 hoursin a saturated solution of Ca7OH)₂ at a temperature of up to 300° C.Then the microspheres were again washed in deionized water andsubsequently dried in an oven at 110° C. Microspheres treated with onlythe deionized water at temperatures of up to 300° C. were employed ascontrols.

Microsphere-filled lightweight cements, used to determine compressivestrength and water permeability, and to explore cement-microsphereinterfaces, were prepared the following way. The lightweight cementslurries, consisting of 30 wt. % class H cement, 10 wt. % silica flour,25 wt. % microspheres [Ca(OH)₂ treated for the cements of the presentinvention and deionized water treated for the controls], and 35 wt. %water were poured into glass test tubes, 3.5--cm diam. by 7.0--cm long.The test tubes were then autoclaved for 24 hours at 300° C.

The chemical states and elemental compositions at the surface sites oftreated and untreated microspheres were identified by precisedeterminations of bonding energies and peak intensities with x-rayphotoelectron spectroscopy (XPS). The spectrometer used was a V. G.Scientific ESCA 3 MK II: the exciting radiation was provided by amagnesium K alpha x-ray source, operated at a constant power of 200 W(10 kV, 20 mA). The vacuum in the analyzer chamber of the instrument wasmaintained at 10⁻⁹ Torr.

The morphological and chemical aspects of the surface and subsurface oftreated microspheres, and the cement hydration products formed in thecement-sphere contact zone were examined with an AMR 100-Å scanningelectron microscope (SEM) associated with TN-2000 energy-dispersivex-ray spectrometry (EDX).

SEM and EDX studies of the surface of the untreated microspheres showedthe surface morphology to be relatively smooth suggesting that they aremostly free of irregularities or deposits. EDX analysis indicates thatthe predominant element present is silicon, with lesser amounts ofaluminum, potassium, and iron and a small quantity of titanium.

FIG. 2 is the XPS spectrum for the unmodified sphere surfaces and itshows the presence of an intense O_(1s) peak and a secondary strongcarbon (C_(1s)) peak. The latter is mainly ascribed to the residualcarbon contaminants. Small aluminum (Al_(2p) and Al_(2s)) and silicon(Si_(2p) and Si_(2s)) signals also were identified. However, the signalintensities of K, Ti, and Fe which were clear on the EDX analysis aretoo weak to be detected on the wide scan at the maximum count rate of10800 C.P.S. Thus, the unmodified sphere surfaces appear to be overlaidwith a thin film consisting of oxidized aluminum, silica glass, and acarbon contaminant. All of the K, Ti, and Fe seem to exist at thesubsurfaces. Such thin surface films are removable.

EDX analysis of the microsphere surface after washing with deionizedwater showed that the originally smooth surface of the "as-received"spheres was transformed into a geometrically reticulated network bywashing at 200° C. This morphological transformation reveals thecharacteristics of the underlying structure and indicates that the thinoverlay can be removed by hot deionized water. The typical networkstructure of lath-like crystals in the underlying material beneath thethin film must be associated with the formation of sillimanite,Al(AlSiO₅), as the major phase of the shell structure. The EDX datasuggests that the underlying crystalline materials contain a largeamount of silicon compounds. No significant changes in peak intensitywere observed for elements such as Al, K, Ti, and Fe.

Compared with the untreated surface, the scan in FIG. 2 (and XPS widescan for the 200° C. deionized water-treated sphere surface) ischaracterized by intense Al, Si, and O signals, the appearance ofidentical K and Fe peaks, and a considerable reduction in C peakintensity. The probable reason for the latter is the elemination ofcarbon contamination by the hot deionized water treatment.

Of particular interest were the morphological transformations whichoccurred on the sphere surfaces modified by the Ca(OH)₂ -saturatedsolution at 100° C. The SEM image exhibited a morphologically peculiarsurface that consisted of a layer of elongated crystals, providingevidence of epitaxial growth of certain hydration products. The epitaxywas topographically indentical to the formation of a continuous layeroverlaid on the sphere surface. The continuous epitaxy film formed ashell structure that encapsulated the sphere particle. The EDX spectrumfor this hydration shell revealed noteworthy reductions in theintensities of the Si, K, Ti, and Fe peaks, a Ca signal, and anunchanged Al peak. The presence of the Ca peak related directly to thereaction products at the interface between the Ca(OH)₂ and the chemicalcomposites of the sphere surface, and the Ca(OH)₂ precipitates on thesphere. The reduction in the peaks for Si, K, Ti, and Fe elementsindicated that the sphere was covered by calcium hydration products to adepth of at least 1 μm. The essentially constant Al intensity for boththe Ca(OH)₂ -and the deionized water treated spheres verified that arelatively large amount of Al was present in the epitaxy layers.

Table 3 summarizes the slurry density measurements, and the densities,compressive strengths, and water permeabilities of the cured specimens.Each value represents the average of three measurements. As expected,the control specimens had a low compressive strength (600 psi) (4.2MPa). This was greatly improved by treatment of the spheres with eitherdeionized water alone or deionized water followed by Ca(OH)₂. Thestrength of the specimens made with deionized water-treated spheresappears to depend on the temperature of the treatment. For example, thestrength developed in the 100° C. deionized water-treated specimens wasconsiderably lower than those at 200° and 300° C. This reduced level ofimprovement might be associated with the presence of a larger amount ofa carbon contaminant on the sphere surface, suggesting that such acontaminant cannot be removed by deionized water at 100° C. Thestrengths for the Ca(OH)₂ sphere-filled specimens appear to be lessdependent on the temperature of the treatment. Here, a maximum strengthof 1440 psi (9.92 MPa) was obtained for the 200° C. Ca(OH)₂ -treatedspecimens. This value corresponds to an improvement in strength ofapproximately 2.4 times above the untreated controls and 1.3 timesgreater than the 300° C. deionized water-treated specimens. It shouldalso be noted that the incorporation of spheres treated with the Ca(OH)₂solution at the high temperature of 300° C. results in a reduction instrength. Therefore, a temperature of up to 200° C. is preferable. Asexpected, an increase in compressive strength results in a reduction inwater permeability. Notably, the water permeability value for the 200°C. Ca(OH)₂ -treated sphere specimens was two orders of magnitude lessthan that for the untreated specimens.

                  TABLE 3                                                         ______________________________________                                        Properties of Untreated and Treated Sphere-Filled                             Lightweight Cementing Materials.                                                       Slur-         300° C.-24 hr autoclaved                                 ry   density  specimen                                                          den-   of set   Compressive                                                                            Water                                     Treatment of                                                                             sity,  cement,  strength,                                                                              permeability,                             microspheres                                                                             g/cc   g/cc     MPa  (psi) darcy                                   ______________________________________                                        Untreated  1.16   0.90     4.20  (610)                                                                              7.86 × 10.sup.-4                  100° C. deionized                                                                 1.16   0.90     4.44  (644)                                                                              --                                      water-treated                                                                 200° C. deionized                                                                 1.17   0.91     7.44 (1080)                                                                              2.48 × 10.sup.-5                  water-treated                                                                 300° C. deionized                                                                 1.19   0.92     7.79 (1130)                                                                              --                                      water-treated                                                                 100° Ca(OH).sub.2 -                                                               1.17   0.91     9.51 (1380)                                                                              --                                      treated                                                                       200° Ca(OH).sub.2 -                                                               1.19   0.91     9.92 (1440)                                                                              5.63 × 10.sup.-6                  treated                                                                       300° Ca(OH).sub.2 -                                                               1.20   0.95     8.68 (1260)                                                                              --                                      treated                                                                       ______________________________________                                    

I claim:
 1. A method of combating lost circulation in a geothermal oroil well which comprises introducing into said well a high temperaturelightweight cement slurry of the H class (API) containing pressureresistant hollow microspheres pretreated by washing and exposing to asolution of an alkali earth metal hydroxide at an elevated temperaturefor a period up to twenty hours.
 2. The method of claim 1 wherein themicrospheres are pretreated with a saturated solution of Ca(OH)₂ atabout 100°-300° C. for up to 20 hours.
 3. The method of claim 2 whereinthe temperature employed is 100° C. and the treatment period is 10hours.